Water-insoluble diphenylamine dyestuffs



, Patented Mar. 24, 1959 U ted States Patent I 2,879,269

2, 79,2 9 wherein x, A and B possess the above-named meanings,

, or, when y represents the direct linkage and R a 4- WATERINSOLUBLE DIPHENYLAMINE halogeno-3'-nitrophenyl radical, with 2 mols of an amino- DYESTUFFS benzene free from water-solubilizing groups and of the Ernest Merian, Bottmingen, Switzerland, assignor, by 5 formula mesne assignments, to Saul & Co., Newark, NJ., as

- H nominee of Fidelity Union Trust Company, executive N trustee under Sandoz Trust (w-z-)..@

No figfgj gf g 1956 10 wherein w, z, m and C possess the above-named meanings. Claims P y, application Switzerland October 1955 The new dyestuffs have not very good building-up- 6 Cl (Cl 260 z39 7) properties from an aqueous dispersion but they are very 1 well suited for dyeing in the mass materials dissolved in The present invention relates to new water-insoluble 15 organic solvents which are subsequently extruded as filadiphenylamine dyestuffs which correspond to the general ment, for example cellulose acetate. As they are well formula soluble in organic solvents, e.g. acetone, the spinning wherein ,0 of masses dyed with them presents no techincal difli- Stands for the direct linkage oxygen the imino or an culties. The solution-dyed shades obtained in this way,

alkylimino group are fast to light, washing, cross dyeing, gas fumes, dry I cleaning and peroxide. The new dyestufis can also be R si gg jgg g g zggi g $21213 22 5 32 employed for coloring plastics of all kinds and for pig- 35 menting lacquers. i' egi' ese lfts zfr r ifiin gl r g g ggfggz xg g g y The reaction of the 1-halegeno-2-n1trobenzene-4-sulstands for the direct carbon linkage or a methylene fonic acid derivatives with the aminobenzenes is con- 1 If sulf xide sulfone ducted advantageously at elevated temperature. Among ethylene vmy oxygen su o the suitable reaction media, those preferred are water or am oxymethylene i 40 an organic solvent, e.g. ethanol, benzyl alcohol, benzene, zstandsfor one ftherad1calS CH2o toluene etc. An addition of a suitable acid-binding --O-CH -O, -O-CH CH --O agent, for example sodium acetate, sodium carbonate or OCH CH -CH -O- sodium bicarbonate, exercises a favorable influence on --O-CH -CH(CH )-O- or condensation in the majority of cases. The same service O-CH(CH )CH --O is performed by an excess of the amine or amines employed in the reaction. W gggi ffig g gzg itg radlcal whlch may bear For use as radicals R which together with y are cam Stands for one of the figures 2, pable of forming a heterocyclic ring, the radicals of the following nitrogen heterocycles enter into consideration: Thiadiazolidine, triazine, triazoline, triazolidine, tetrazine, oxazolidine, thiazolidine, imidazoline, imidazolidine, pyrrole, pyrrolidine, oxadiazine, thiadiazine, pentoxazoline, pentoxazolidine, morpholine, homomorpholine, penthiazoline, m-thiazane, thiamorpholine, pyrimidine, pyrazine and piperidine.

The 1-halogeno-2-nitrobenzene-4-sulfonic acid derivatives used according to the present definition as starting products can be produced by known methods from 1- halogeno-Z-nitrobenzenes by the introduction of the suband ri stands for 0 or 1,

and in which the nuclei A, B and C may contain further substitueuts such as fluorine, chlorine, bromine, alkyl containing at most 18 carbon atoms, mononuclear aryl, cyclohexyl, benzyl, trifiuoromethyl and acylamino, acyl being carboxylic acid acyl.

The process for their production consists in reacting, preferably in presence of an acid-binding agent, 1 mol of a 1-halogeno-2-nitrobenzene-4-sulfonic acid derivative of stituted ulf i acid radical or by nitration f h 1- the formula halogenobenzene-4-sulfonic acid derivative. Of especial interest are l-halogeno-2-nitrobenzene-4-sulfonic acidl :-1I arylesters, -arylamides, -cycloalkylamides, -alkylaryl- No I amides, -morpholides, -oxazolidides or -oxazides, 4-

.halogeno 3 nitro 1.1 diphenylsulfones and 4.4- wherein Hal stands for chlorine or bromine, and y and dihalogeno-3.3-dinitro-1.1-diphenylsulfones.

Rpossess the above-named meanings, with 1 mol of an The aminobenzenes of the general formula aminobenzene free from water-solubilizing groups, which NH: has 'the formula NH: 7Q

which are used according to the invention may be further substituted. In particular, they may contain alkyl, aryl,

. 3 aralkyl or cycloalkyl radicals, halogen atoms, trifluoromethyl groups or acylamino groups. Examples of those which find employment are 4-amino-1.1'-diphenylester or. -thioether, 4-amiuo-4-butyl-1.lfidiphenylether or -thioether, 4 .amino 4 octyl 1.1 diphenylether or -thioether, 4-amino-4-cyclohexyl-1.l'adiphenylether or -.thioether, 4.-amino-2',4-dichloro-l.1-diphenylether .or -thioether, 4-amino-2,4',S-trichloro-l.1'-diphenylether or -thioether, 4-amino-l-benzylphenylether or -thioether and their 2-halogeno-deriyatives, 4-amino-1.1-diphenylmethane, 4 amino 1.1 diphenylethane, 4-amino l.1'-stilbene, 4-amino-2.2-dichloro-1.1'-stilbene, 4-amino-4- acetylamino 1.1 diphenyl, 4 amino 4' acetylamino 3.3 dimethoxy 1.1 diphenyl, 1 amino- 3 phenoxymethyl 4 methylbenzene, 4 amino 1.1- azobenzene or 4-amino-3.2'-dimethyl-1.1-azobenzene. Especially interesting are amines which are substituted by alkyl radicals containing if desired ether groups.

Examples of suitable amines corresponding, according to the invention, to the general formula are: 1-(2'-hydroxy)-ethoxy-2- or -3- or -4-aminobenzene, 1-(2'-methoxy or -ethoxy or -propoxy or -butoxy)-ethoxy 2- or -3- or -4-aminobenzene, 1-[2-(2"-hydroxy)-ethoxy]- ethoxy-Z- or -3- or -4-aminobenzene, 1-[2-(2"-methoxy or -ethoxy or -propoxy or -butoxy)-ethoxy}-ethoxy-2- or -3- or -4-aminobenzene, 1-{2'-[2"-(2'-hydroxy)-ethoxy]- ethoxy}-ethoxy-2- or -3- or -4-aminobenzene, 1-[2- or 3'-(2- or 3"-hydroxy)-propoxy]-propoxy-4-aminoben- Zene, -1-[2-(2"rhydroxy)-ethoxy]-ethoxy-3-acety1amino- 6-aminobenzene, 1-(2.3'-dihydroxy)-propoxy-2- or'-3- or -4-aminobenzene, l-methoxymethylor l-ethoxymethyl-Z- or 3- or -4-aminobenzene, 1-(2-l1ydroxy)-ethoxymethyl- 2- or -3 or -4-aminobenzene, l-(2-rnethoxy or -ethoxy)- ethoxymethyl-2- or -3- or -4-aminobenzene, 1-[2'-(2"- hydroxy)-cthoxy]- ethoxymethyl- -2- or -3- or -4-arninobenzene, 1-(2'-hydroxy-ethoxymethyl- 3-amino-6-methylbenzene, 1.5-bis-[(2-hydroxy)-ethoxymethyl]-3-an1ino-6- methylbenzene and 1-[2'-(2"-methoxy or -ethoxy or -pro-' poxy or -butoxy) ethoxy] ethoxymethyl 3 amino- 6-methylbenzene.

The following examples illustrate the invention. All parts specified therein are by weight; the temperatures are given in degrees centigrade.

EXAMPLE 1 10.5 parts of 1-chlor0-2-nitrobenzene-4-sulfonic acid phenyl amide, 10.1 parts of 4-amino-4'-octyl-l.l-diphenyl ether, 3 parts of sodium bicarbonate and 50 parts of water are heated to the boil with stirring. The resulting emulsion turns a deep yellow in color; after /2 hours it is cooled and adjusted with hydrochloric acid to react-acid to congo paper. After some time the dycstuft thus formed solidifies and can be isolated by filtering and washing with water. Upon recrystallization from ethanol it melts at 151-152. The new dyestufi dyes cellulose acetate in the mass in very fast reddish yellow shades.

' EXAMPLE 2 When the 10.5 parts of 1-chloro-2-nitrobenzene-4- sul-. fonic acid phenyl amide of Example 1 are replaced by 11.7 parts of l-bromo-2-nitrobenzene-4-sulfonic acid morpholide and the 10.1 parts of 4-amino-4'-octyl-1.ldiphenyl ether by 11.2 parts of 4-amino-2-chloro-4-tert. butyl-l.1'-diphenyl ether, a yellow dyestufi is obtained which melts at l36139.

EXAMPLE 3 9.6 parts of l-chloro-2-nitrobenzene-4-sulfonic aciddi-(2'-hydroxyethyl)-amide, 7.5 parts of 4-amino-4-tert. butyl-l.1-diphenyl ether, 3 parts ,of sodium bicarbonate and-'SOpartSWf'Water arebo'iledfor 4 hours with rer 4 flux. Upon cooling, the aqueous phase is decanted from the oily precipitated dyestutf and the dark brown oil dissolved in 50 parts of ethanol. After some time the sulfonic acid morpholide .dyestufi, which is formed by ring closure during condensation and is poorly soluble in ethanol, .is precipitated. It is filtered 01f, Washed with ethanol and dried. It melts at 168-170, is poorly soluble in ethanol and readily soluble in benzene.

In. the following table further dyestuffs obtainable accordingto the particulars given in Examples 1 t0.3 are enumerated. They correspond to the formula and are characterized by the radical R the basic compound R H of the radical R their melting points, and the color of their solutions in acetone.

Table Melting Color 0! Exam- Rr-H R: Point, Solution ple N0. 0. ,inAcetone 4 phenylomtne 4'-tert.butyl- 148-151 yellow.

phenoxy.

5.; N-ethylphenyl- 4'-octylphenoxy... 120-124 Do.

amine.

0 2.5-dlchlorophen- .do 171-173 Do.

ylnmlne.

7 3.4-dlchlorophendo 173-178 Do.

ylamine.

8 2.3-tetramethyldo 202-200 Do.

enephenylamino.

0 1-naphthylamtne do Do.

10 morphollne do. 138-141 Do.

11 do 4-cyclohexyl- 215-217 D'o.

: phenoxy.

' 2'.4'.5'trichloro- 177-181 Do.

phenoxy. benzylo 174-179 D0. phenylazo-- 148-152 Do. 4-octylphenox 96-100 D0. phenol do 98-100 D0. d1-(2-ethy1hexyD- 4'-phenylphenoxy D0.

amine.

18 N-hydroxyethylphenyl 136-140 Do.

phenylamine.

EXAMPLE 19 The acetone-solubility of Examples 11, 12 and 13 is of the order of about 2%. When 10.2 parts of 1-chloro-2- nitrobenzene-4-sulfonic acid morpholide are condensed in an analogous manner with a mixture of 3.7 parts of 4-amino-4'-cyclohexyl-1.1'-diphenylether, 2 'parts of 4-amino-2',4,5-trichloro-l.l'-dipheny1ether and 2.8 parts of 4-aminophenyl-l-benzylether, a dyestutf mixture is obtained which exhibits substantially better acetone-solubility while possessing the same fastness properties as the earlier-cited examples. The freezing point of the mixture is EXAMPLE 20 12 parts of 1-chloro-2-nitrobenzene-4sulfonic acid N-hydroxyethylphenyl amide and 6.2 parts of 4-amino- 1.1'-diphenylether are reacted as described in Example 1. Itis possible to arrive at the same dyestuff when afsolution of 46.1 parts of 4phenoxy-2'-nitro-l.1'-diphenylamine- 4'-sulfonic acid phenylamide and 4.2 parts of caustic soda in 1000 parts of water at is drop-fedwith 9.5 parts of ethylene chlorohydrine. The melting point of the product is 159-163.

EXAMPLE 21 12.5 a parts of 4.4-dichloro-3.3-dinitro-1.1'-diphenylsulfone, 18 parts of 4-[2'-(2"-methoxy)-ethoxyl-ethoxyl-arninobenzene, 6 parts of sodium bicarb0nate, 300 p'art s of ethanol and 30 parts of water are boiled for 6 hours with reflux. Upon cooling the dyestuif is precipitated. It

5 EXAMPLE 22 18.8 parts of 4.4-dichloro-3.3'-dinitro-l.l'-diphenylsulfone,'32 parts of 1-amino-4-(2'-hydroxy)-ethoxybenzene and 250 parts of ethanol are boiled for hours with reflux. Upon cooling the dicondensed dyestuff is precipitated. It is filtered and washed with ethanol, excess amine thereby being brought into solution. By recrystallization from ethanol the new dyestulf is obtained in the pure state having a melting point of 192195. This compound is practically insoluble in benzene, but fairly well soluble in acetone.

EXAMPLE 23 A mixture of 18.4 parts of 4.4'-diamin0-l.1-diphenyl, 75 parts of 1-chloro-2-nitrobenzene-4-sulionic acid N-ethyl-N-phenyl amide, 17 parts of sodium bicarbonate, 700 parts of ethanol and 50 parts of water are boiled for 6 hours with reflux. It is then allowed to cool and the precipitated reaction product filtered. The filtrate is a mixture, the greater part of which consists of the monocondensed product of the formula which has a melting point at 192 196", and the lesser part of, the dicondensed product whose melting point is 226228. The two dyestulfs can be separatedby, e. g. boiling with ethanol, but only the monocondensed dyestufi is sufficiently soluble in acetone to be suitable for dyeing cellulose acetate in the dope.

EXAMPLE 24 25 parts of 4.4'-diamino-1.1'-dipheny1sulfone, 68 parts of 1-chloro-2-nitrobenzene-4-sulfonic acid N-ethyl-N- phenylamide, 17 parts of sodium bicarbonate, 50 partsof water and 400 parts of ethylene glycol are boiled for 20 hours with reflux. Upon cooling the reaction product is filtered ofi and recrystallized from ethanol. Pale yellow needles with melting point 139-145 are obtained.

"Other dyestuffs according to the invention which are suited for dyeing in the mass materials dissolved in organic solvents which are subsequently extruded as filament and specially cellulose acetate in yellow shades fast to light, washing, cross dyeing, gas fumes, dry cleaning and peroxide are:

EXAMPLE 25 2-nitro-4'-(4"-butyl) phenoxydiphenylamine 4 sulfonic acid-1"'.3"'-oxazolidide;

EXAMPLE 26 2-nitro-4'-(4"-buty1) phenoxydiphenylamine 4 sulfonic acid-5"'-methyl-1"'.3"-oxazolidide;

EXAMPLE 27 2-nitro-4'-(4-butyl) phenoxydiphenylamine 4 sulfonic acid-1"'.3"'-oxazide;

2-'nitro-4-(4"-butyl) phenoxydiphenylamine 4 sulfonic acid-(N-ethyl) -phenylamide;

EXAMPLE 3O 2-nitro-4'-(4"-butyl) phenoxydiphenylamine 4 sulfonic acid-(N-hydroxyethyl) -phenylamide;

EXAMPLE 31 2-nitro-4-(4"-butyl) phenoxydiphenylamine-4 sul- I ionic acid (N-hydroxypropyl) -phenylamide;

7 Tonic acid-cyclohexylamide;

6 EXAMPLE 32 2-nitro-4'-(4"-butyl) phenoxydiphenylamine 4 sulfonic acid-phenyl ester;

EXAMPLE 33 2-nitro-4'-(4"-butyl) phenoxydiphenylamine 4 sulfonic acid-cyclohexyl amide;

EXAMPLE 34 2-nitro-4'-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-morpholide;

EXAMPLE 35 2-nitro-4'-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-phenylamide;

EXAMPLE 36 2-nitro 4-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-1".3-oxazolidide;

EXAMPLE 37 2-nitro-4'-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-5"'-methyl-1.3'-oxazolidide;

EXAMPLE 3 8 2-nitro4-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-l"'.3"'-oxaz ide;

EXAMPLE 39 2-nitro4'-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-(N-methyl)-phenylamide;

EXAMPLE 4O 2-nitro-4'-(4"-amyl) phenoxydiphenylamine 4 sulfonic acid-(N-ethyl)-phenylamide;

EXAMPLE 41 2-nitro-4-(4"-amyl) phenoxydiphenylamine 4 sul .fonic acid- (N-hydroxyethyl) -phenylamide;

EXAMPLE 4;

2-nitro-4-(4-amyl) phenoxydiphenylamine 4 sulionic acid-(N-hydroxypropyl) -phenylamide;

EXAMPLE43 2-nitro-4'-(4 -amyl) phenoxydiphenylamine 4 sulionic aci-d-phenyl ester;

EXAMPLE 44 2-nitro-4'-'('4"-amyl) phenoxydiphenylamine 4 sul- EXAMPLE 45 2-nitro-4'-(4"-octyl) phenoxydiphenylamine 4 sulfonic acid-1".3"-oxazolidide;

EXAMPLE 46 2-nitro-4'-(4"-octyl) phenoxydiphenylamine 4 sulfonic acid-5""-methyl-l-".3"-oxazolidide;

EXAMPLE 47 2nitro-4'-(4"-octyl)' phenoxydiphenylamine 4 sulfonic acid-l"'.3"'-oxazide;

EXAMPLE 48 2-nitro-4'-(4"-octyl) phenoxydiphenylamine 4 sulfonic .acid-(N-methyl) -phenylamide;

EXAMPLE 49 2-nitro-4'-(4"-octyl) phenoxydiphenylamine 4 sulfonic acid- (N-propyl) -phenylamide;

EXAMPLE 50 2-nitro-4'-(4"-octyl) phenoxydiphenylamine 4 sub tonic acid-(N-hydroxyethyl)-phenylamide;

'7 EXAMPLE -51 "2-nitro-4'-(4"-octyl) phenoxydiphenylamine 4 sulfonie acid-(N-hydroxypropyl) -phenylarnide;

8. EXAMPLE 67 2nitr o-.4'-phenyldiphenylamine 4 sulfonie acid-di-nhexylamide;

EXAMPLE 52 EXAMPLE 68 Z-nitro 4' (2.4"-dibutyl)-phenoxydiphenylamine-4- 2 i qe y )-p g p y 4 sulfonic acid-(N-ethyl)-phenylamide; fonie acidv-di-n-octadecylamide;

EXAMPLE 53 EXAMPLE 69 Z-nitro 4 (2".4"-diamyl)-phenoxydiphenylamine-4- 2-nitro-3'-bromo 4' (4" amyl) phenoxydiphenylsulfonic acid-morpholide; amine-4-sulfonic acid-'(2".6"'-dimethyl)-morpholide;

EXAMPLE 54 EXAMPLE 7() -n t y l)- Y P Y 2-nitro-3'-fluo ro 4' 4" methyl)-phenoxydiphenylsulfomo acid-l .3 -oxazol1dide; a in -4- ]f ni acid naphthyl ester;

EXAMPLE 55 EXAMPLE 71 1 h d" h lam'ne-4- sui ro iii z aciri-uiimil)i iiilll i 1p any 1 mm )-P h .,.4

4-sulfonic acid-(N-2"-ethylhexyl)-phenylamide; EXAMPLE v56 3.3'-dinitro-4.4'-bis-{(p-rnethoxyethoxy)-phenylamino]- E: a u [PLE 72 1.1'-diphenylsulf0ne; Z-nitro 4' (4" amyloxy)-phenoxydiphenylamine-4- EXAMPLE 57 sulfonic aeid-(N-methyl)-phenylamide;

3.3'-dinitro-4.4-bis-[(p ethoxyethoxy) phenylamino} EXAMPLE 73 Lndlphenylsulfone; so Z-nitro 4'-(4' '-dodecyl)-phenoxydiphenylamine-4-sul- EXAMPLE 58 fonic acid-(N-methyl)-phenylamide;

3.3-dinitro 4.4 bis-[p-butoxyethoxy)-phenylamino]- EXAMPLE 74 'dlphenylsulfone; Z-nitro 4' (4" nonyl)-phenonydiphenylamine-4-sul- EXAMPLE 59 fonic aeid-(N-butyl)-phenylamide;

3.3 dinitro 4.4 bis [(p-methoxyethoxyethoxy-lchloro)-phenylamino]-l.l-diphenylsulfone; MPLE 75 EXAMPLE 60 2-nitro-4f(4"-octadecyl)-phenoxydiphenyl amine-4-sultonic acid-a-naphthylamide; 2-nitrd4"phenyldiphenylamme 4 sulfomc acid-(N- ethyl)-phenylamide; EXAMPLE 76 EXAMPLE 61 2-nitro-4'-(4"- amyl)-phenoxydiphenylamine-4-sulfonic Z-nitro-4'-phenylthiodiphenylamine-l-sulfonic acid-(N- "methyl)'phenyl ester- 4 1f 100 parts of cellulose acetate are dissolved in 300 parts g ggj izg fig omc acld of solvent (93% acetone, 7% methanol); the solution is EXAMPLE 63 mixed for a short time and left overnight to swell. 1 part of the dyestufi obtainable according to Example Emilio-4' y jy p y 4 Sulfomc acid 5 is dissolved in 85 parts of the solvent by simple agitation, ethyU-phenylamKie; and this solution run into the cellulose acetate solution. EXAMP E 6 The mixture is stirred in an open vessel until parts of -2-nitro-4'-(4"-acetylamino) phenylidiphenylamine 4- the solvent have YaP F Sammie acid (N ethy1)Thewlamide; 55 The dyed mass 18 fed mto the spinning pot and extruded 1n the normal manner. The resulting filament is EXAMPLE 65 readv for further processing. It is fast to light, boiling, 2-nitro 4' (3" trifiuoromethyl) phenoxydiphenylalkali, a h grass y ng, y Fleming, fumes amine-4-sulfonic acid-(N-butyl)-cyclohexylamide; hydrolsulfite, p g bleachmg, oxallc a p p ati n,

50 wet p eating, su imation, sea water, water, washing, rub- EXAMPLE 66 bing and peracetic acid bleaching. 2-nitro-4-phenyldiphenylamine-4-sulfonic acid-(N-2"- Formulae of representative dyestuffs of the foregoing ethylhexyl)-cyclohexylamide; examples are as follows:

EXAMPLE 5 0 (EH: (I311: N /CHs-CH: on; em O EXAMPLE 10 EXAMPLE 1:! 0:|N A OH! CH1 7 H.o a cH. a 0 NHOo. NH@

(3H1 (EH: 7

EXAMPLE 21 0m N0, I EHPCHr-OONHO-SOFONHGO-CflrCHPE EXAMPLE 29 v OaN EXAMPLE s9 7 osN- OH: CE;

I, EMF 0 NH SOx-N F l EXAMPLE 40 (MN OHl CH3 CH:

BOPN

MtHPt O NHO EXAMPLE 82 om CH! 7 maagogmcaopo j EXAMPLE 33 OaN lH: Having thus .disclosed invenfim? what is claimed is: where R isa member selected from the class consisting 1. A water-msoluble drphenylamme dyestufi of the 15 cf phenylimim, N. thy1.phenylimino, N-ethyl-phenylfmmula imino, hexahydrophenylimino, morpholino, 1,3-oxazino, 5-methy1-1,3-oxazolidino, 1,3-oxazolidino, and phenoxy.

2. The water-insoluble diphenylamine dyestuff which M -G O BOr-R! corresponds to the formula OaN (EH; CH: /CHy-CH: mcc-cH=- :oO-NH sot-N H: ('JHI C 3. The water-insoluble diphenylamine dyestuff which corresponds to the formula 4. The water-insoluble diphenylamine dyestutr which corresponds to the formula 6. The water-insoluble diphenylamine dyestufi' which corresponds to the formula om ON on on a Biol-C O NH O:N 0

| CH: CHI-C References Cited in the file of this patent UNITED STATES PATENTS 2,725,390 Fogelman et a1. Nov. 29, 1955 FOREIGN PATENTS 504,428 Canada July 24, 1954 

1. A WATER-INSOLUBLE DIPHENYLAMINE DYESTUFF OF THE FORMULA
 6. THE WATER-INSOLUBLE DIPHENYLAMINE DYESTUFF WHICH CORRESPONDS TO THE FORMULA 